Interfacial energetics of silicon in contact with 11 M NH 4F(aq), buffered HF(aq), 27 MHF(aq), and 18 M H 2so 4

David J. Michalak, Florian Gstrein, Nathan S Lewis

Research output: Contribution to journalArticle

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Abstract

Open-circuit impedance spectra, channel impedance spectroscopy on solution-gated field-effect devices, and differential capacitance vs potential (Mott-Schottky) measurements were used to determine the energetics of n-Si(111), n-Si(100), and p-Si(111) electrodes in contact with aqueous 11 M (40% by weight) NH 4F, buffered HF (BHF), 27 M (48%) HF(aq), and concentrated (18 M) H 2SO 4. A Mott-Schottky analysis of A s 2C sc -2-vs-E (where A s is the interfacial area, and C sc is the differential capacitance as a function of the electrode potential, E) data yielded reliable barrier heights for some silicon/liquid contacts in this work. Performing a Mott-Schottky analysis, however, requires measurement of the differential capacitance under reverse bias, where oxidation or etching can occur for n-Si and where electroplating of metal contaminants can occur for p-Si. Hence, open-circuit methods would offer desirable, complementary approaches to probing the energetics of such contacts. Accordingly, open-circuit, near-surface channel conductance measurements have been performed using solution-gated n +-p-Si(111)-n + and p +-n-Si(100)-p + devices. Additionally, opencircuit impedance spectra were obtained for silicon electrodes in contact with these solutions, The combination of the three techniques indicated that the surfaces of n-Si(111) and n-Si(100) were under accumulation when in contact with either 11 M NH 4F(q) or BHF(aq). The barrier heights for n-Si(111) and n-Si(100) in 11 M NH 4F(aq) were -0.065 ±0.084 V and -0.20 ±0.21 V, respectively, and were -0.03 ±0.19 V and -0.07 ± 0.24 V, respectively, for these surfaces in contact with buffered HF(aq). Consistently, p-Si(111) surfaces were determined to be in inversion in contact with these electrolytes, exhibiting barrier heights of 0.984 ± 0,078 V in contact with 11 M NH 4F(aq) and 0.97 ±0.22 V in contact with buffered HF(aq). In contact with 27 M HF(aq), n-Si(111) and n-Si(100) were in depletion, with barrier heights of 0.577 ±0.038 V and 0.400 ± 0.057 V, respectively, and p-Si(111) was under inversion with a barrier height of 0.856 ±0.076 V. Measurements performed in 18 M H 2SO 4 revealed barrier heights of 0.75 ±0.11 V, 0.696 ±0.043 V, and 0.889 ±0.018 V for n-Si(111), n-Si(100), andp-Si(111), respectively, demonstrating that in 18 M H 2SO 4, the band edge positions of Si were different for different doping types. The barrier height data demonstrate that the observed low recombination rates of silicon in contact with 11 M NH 4F, BHF, or 18 M H 2SO 4 cannot necessarily be attributed to a reduction in the number of surface trap states. In part, low surface recombination rates are expected for such systems because the very large or very small barrier height for silicon in contact with these liquids provides a potential barrier that prevents one type of photogenerated carrier (either electons or holes) from reaching the surface, thereby producing a low steady-state surface recombination rate.

Original languageEnglish
Pages (from-to)16516-16532
Number of pages17
JournalJournal of Physical Chemistry C
Volume111
Issue number44
DOIs
Publication statusPublished - Nov 8 2007

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Silicon
silicon
Contacts (fluid mechanics)
Capacitance
Electrodes
capacitance
Networks (circuits)
impedance
electrodes
Liquids
inversions
Surface states
Electroplating
Electrolytes
electroplating
Etching
liquids
Metals
Doping (additives)
Spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Interfacial energetics of silicon in contact with 11 M NH 4F(aq), buffered HF(aq), 27 MHF(aq), and 18 M H 2so 4 . / Michalak, David J.; Gstrein, Florian; Lewis, Nathan S.

In: Journal of Physical Chemistry C, Vol. 111, No. 44, 08.11.2007, p. 16516-16532.

Research output: Contribution to journalArticle

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abstract = "Open-circuit impedance spectra, channel impedance spectroscopy on solution-gated field-effect devices, and differential capacitance vs potential (Mott-Schottky) measurements were used to determine the energetics of n-Si(111), n-Si(100), and p-Si(111) electrodes in contact with aqueous 11 M (40{\%} by weight) NH 4F, buffered HF (BHF), 27 M (48{\%}) HF(aq), and concentrated (18 M) H 2SO 4. A Mott-Schottky analysis of A s 2C sc -2-vs-E (where A s is the interfacial area, and C sc is the differential capacitance as a function of the electrode potential, E) data yielded reliable barrier heights for some silicon/liquid contacts in this work. Performing a Mott-Schottky analysis, however, requires measurement of the differential capacitance under reverse bias, where oxidation or etching can occur for n-Si and where electroplating of metal contaminants can occur for p-Si. Hence, open-circuit methods would offer desirable, complementary approaches to probing the energetics of such contacts. Accordingly, open-circuit, near-surface channel conductance measurements have been performed using solution-gated n +-p-Si(111)-n + and p +-n-Si(100)-p + devices. Additionally, opencircuit impedance spectra were obtained for silicon electrodes in contact with these solutions, The combination of the three techniques indicated that the surfaces of n-Si(111) and n-Si(100) were under accumulation when in contact with either 11 M NH 4F(q) or BHF(aq). The barrier heights for n-Si(111) and n-Si(100) in 11 M NH 4F(aq) were -0.065 ±0.084 V and -0.20 ±0.21 V, respectively, and were -0.03 ±0.19 V and -0.07 ± 0.24 V, respectively, for these surfaces in contact with buffered HF(aq). Consistently, p-Si(111) surfaces were determined to be in inversion in contact with these electrolytes, exhibiting barrier heights of 0.984 ± 0,078 V in contact with 11 M NH 4F(aq) and 0.97 ±0.22 V in contact with buffered HF(aq). In contact with 27 M HF(aq), n-Si(111) and n-Si(100) were in depletion, with barrier heights of 0.577 ±0.038 V and 0.400 ± 0.057 V, respectively, and p-Si(111) was under inversion with a barrier height of 0.856 ±0.076 V. Measurements performed in 18 M H 2SO 4 revealed barrier heights of 0.75 ±0.11 V, 0.696 ±0.043 V, and 0.889 ±0.018 V for n-Si(111), n-Si(100), andp-Si(111), respectively, demonstrating that in 18 M H 2SO 4, the band edge positions of Si were different for different doping types. The barrier height data demonstrate that the observed low recombination rates of silicon in contact with 11 M NH 4F, BHF, or 18 M H 2SO 4 cannot necessarily be attributed to a reduction in the number of surface trap states. In part, low surface recombination rates are expected for such systems because the very large or very small barrier height for silicon in contact with these liquids provides a potential barrier that prevents one type of photogenerated carrier (either electons or holes) from reaching the surface, thereby producing a low steady-state surface recombination rate.",
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AU - Lewis, Nathan S

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N2 - Open-circuit impedance spectra, channel impedance spectroscopy on solution-gated field-effect devices, and differential capacitance vs potential (Mott-Schottky) measurements were used to determine the energetics of n-Si(111), n-Si(100), and p-Si(111) electrodes in contact with aqueous 11 M (40% by weight) NH 4F, buffered HF (BHF), 27 M (48%) HF(aq), and concentrated (18 M) H 2SO 4. A Mott-Schottky analysis of A s 2C sc -2-vs-E (where A s is the interfacial area, and C sc is the differential capacitance as a function of the electrode potential, E) data yielded reliable barrier heights for some silicon/liquid contacts in this work. Performing a Mott-Schottky analysis, however, requires measurement of the differential capacitance under reverse bias, where oxidation or etching can occur for n-Si and where electroplating of metal contaminants can occur for p-Si. Hence, open-circuit methods would offer desirable, complementary approaches to probing the energetics of such contacts. Accordingly, open-circuit, near-surface channel conductance measurements have been performed using solution-gated n +-p-Si(111)-n + and p +-n-Si(100)-p + devices. Additionally, opencircuit impedance spectra were obtained for silicon electrodes in contact with these solutions, The combination of the three techniques indicated that the surfaces of n-Si(111) and n-Si(100) were under accumulation when in contact with either 11 M NH 4F(q) or BHF(aq). The barrier heights for n-Si(111) and n-Si(100) in 11 M NH 4F(aq) were -0.065 ±0.084 V and -0.20 ±0.21 V, respectively, and were -0.03 ±0.19 V and -0.07 ± 0.24 V, respectively, for these surfaces in contact with buffered HF(aq). Consistently, p-Si(111) surfaces were determined to be in inversion in contact with these electrolytes, exhibiting barrier heights of 0.984 ± 0,078 V in contact with 11 M NH 4F(aq) and 0.97 ±0.22 V in contact with buffered HF(aq). In contact with 27 M HF(aq), n-Si(111) and n-Si(100) were in depletion, with barrier heights of 0.577 ±0.038 V and 0.400 ± 0.057 V, respectively, and p-Si(111) was under inversion with a barrier height of 0.856 ±0.076 V. Measurements performed in 18 M H 2SO 4 revealed barrier heights of 0.75 ±0.11 V, 0.696 ±0.043 V, and 0.889 ±0.018 V for n-Si(111), n-Si(100), andp-Si(111), respectively, demonstrating that in 18 M H 2SO 4, the band edge positions of Si were different for different doping types. The barrier height data demonstrate that the observed low recombination rates of silicon in contact with 11 M NH 4F, BHF, or 18 M H 2SO 4 cannot necessarily be attributed to a reduction in the number of surface trap states. In part, low surface recombination rates are expected for such systems because the very large or very small barrier height for silicon in contact with these liquids provides a potential barrier that prevents one type of photogenerated carrier (either electons or holes) from reaching the surface, thereby producing a low steady-state surface recombination rate.

AB - Open-circuit impedance spectra, channel impedance spectroscopy on solution-gated field-effect devices, and differential capacitance vs potential (Mott-Schottky) measurements were used to determine the energetics of n-Si(111), n-Si(100), and p-Si(111) electrodes in contact with aqueous 11 M (40% by weight) NH 4F, buffered HF (BHF), 27 M (48%) HF(aq), and concentrated (18 M) H 2SO 4. A Mott-Schottky analysis of A s 2C sc -2-vs-E (where A s is the interfacial area, and C sc is the differential capacitance as a function of the electrode potential, E) data yielded reliable barrier heights for some silicon/liquid contacts in this work. Performing a Mott-Schottky analysis, however, requires measurement of the differential capacitance under reverse bias, where oxidation or etching can occur for n-Si and where electroplating of metal contaminants can occur for p-Si. Hence, open-circuit methods would offer desirable, complementary approaches to probing the energetics of such contacts. Accordingly, open-circuit, near-surface channel conductance measurements have been performed using solution-gated n +-p-Si(111)-n + and p +-n-Si(100)-p + devices. Additionally, opencircuit impedance spectra were obtained for silicon electrodes in contact with these solutions, The combination of the three techniques indicated that the surfaces of n-Si(111) and n-Si(100) were under accumulation when in contact with either 11 M NH 4F(q) or BHF(aq). The barrier heights for n-Si(111) and n-Si(100) in 11 M NH 4F(aq) were -0.065 ±0.084 V and -0.20 ±0.21 V, respectively, and were -0.03 ±0.19 V and -0.07 ± 0.24 V, respectively, for these surfaces in contact with buffered HF(aq). Consistently, p-Si(111) surfaces were determined to be in inversion in contact with these electrolytes, exhibiting barrier heights of 0.984 ± 0,078 V in contact with 11 M NH 4F(aq) and 0.97 ±0.22 V in contact with buffered HF(aq). In contact with 27 M HF(aq), n-Si(111) and n-Si(100) were in depletion, with barrier heights of 0.577 ±0.038 V and 0.400 ± 0.057 V, respectively, and p-Si(111) was under inversion with a barrier height of 0.856 ±0.076 V. Measurements performed in 18 M H 2SO 4 revealed barrier heights of 0.75 ±0.11 V, 0.696 ±0.043 V, and 0.889 ±0.018 V for n-Si(111), n-Si(100), andp-Si(111), respectively, demonstrating that in 18 M H 2SO 4, the band edge positions of Si were different for different doping types. The barrier height data demonstrate that the observed low recombination rates of silicon in contact with 11 M NH 4F, BHF, or 18 M H 2SO 4 cannot necessarily be attributed to a reduction in the number of surface trap states. In part, low surface recombination rates are expected for such systems because the very large or very small barrier height for silicon in contact with these liquids provides a potential barrier that prevents one type of photogenerated carrier (either electons or holes) from reaching the surface, thereby producing a low steady-state surface recombination rate.

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